An efficient synergistic catalyst, AgPd bimetal supported on metal–organic framework derived porous carbon (AgPd/MOF-5-C), was fabricated for the first time. The catalyst exhibited 100% H2 selectivity and high catalytic activity in hydrogen generation from formic acid at ambient conditions. The initial turnover frequency could reach as high as 854 h− 1. The combination of distinct interaction among bimetal, support and high dispersion of nanoparticles drastically enhances the catalytic performance of the resulted catalyst.